Crevice steels

Crevice corrosion of unalloyed steel in near-neutral water, (a) Behavior of "un-creviced" steel surface in aerated and deaerated water, (b) Behavior in presence of crevice—role of IR drop. 

Ma.rine. In the presence of an electrolyte, eg, seawater, aluminum and steel form a galvanic cell and corrosion takes place at the interface. Because the aluminum superstmcture is bolted to the steel bulkhead in a lap joint, crevice corrosion is masked and may remain uimoticed until replacement is required. By using transition-joint strips cut from explosion-welded clads, the corrosion problem can be eliminated. Because the transition is metaHurgicaHy bonded, there is no crevice in which the electrolyte can act and galvanic action caimot take place. Steel corrosion is confined to external surfaces where it can be detected easily and corrected by simple wire bmshing and painting. 

Crevice Corrosion. Crevice corrosion is intense locali2ed corrosion that occurs within a crevice or any area that is shielded from the bulk environment. Solutions within a crevice are similar to solutions within a pit in that they are highly concentrated and acidic. Because the mechanisms of corrosion in the two processes are virtually identical, conditions that promote pitting also promote crevice corrosion. Alloys that depend on oxide films for protection (eg, stainless steel and aluminum) are highly susceptible to crevice attack because the films are destroyed by high chloride ion concentrations and low pH. This is also tme of protective films induced by anodic inhibitors. 

The stainless steels contain appreciable amounts of Cr, Ni, or both. The straight chrome steels, types 410, 416, and 430, contain about 12, 13, and 16 wt % Cr respectively. The chrome—nickel steels include type 301 (18 wt % Cr and 9 wt % Ni), type 304 (19 wt % Cr and 10 wt % Ni), and type 316 (19 wt % Cr and 12 wt % Ni). Additionally, type 316 contains 2—3 wt % Mo which gready improves resistance to crevice corrosion in seawater as well as general corrosion resistance. AH of the stainless steels offer exceptional improvement in atmospheric conditions. The corrosion resistance results from the formation of a passive film and, for this reason, these materials are susceptible to pitting corrosion and to crevice corrosion. For example, type 304 stainless has very good resistance to moving seawater but does pit in stagnant seawater. 

In the stainless group, nickel greatly improves corrosion resistance over straight chromium stainless. Even so, the chromium-nickel steels, particularly the 18-8 alloys, perform best under oxidizing conditions, since resistance depends on an oxide film on the surface of the alloy. Reducing conditions and chloride ions destroy this film and bring on rapid attack. Chloride ions tend to cause pitting and crevice... 

These alloys have extensive applications in sulfuric acid systems. Because of their increased nickefand molybdenum contents they are more tolerant of chloride-ion contamination than standard stainless steels. The nickel content decreases the risk of stress-corrosion cracking molybdenum improves resistance to crevice corrosion and pitting. 

These reactions are shown schematically near a crevice in Fig. 2.2. Many other reactions may occur at anodes and cathodes, but Reactions 2.1 and 2.2 predominate on carbon steel, for example, in near neutral pH, oxygenated water. 

Oxygen concentration is held almost constant by water flow outside the crevice. Thus, a differential oxygen concentration cell is created. The oxygenated water allows Reaction 2.2 to continue outside the crevice. Regions outside the crevice become cathodic, and metal dissolution ceases there. Within the crevice. Reaction 2.1 continues (Fig. 2.3). Metal ions migrating out of the crevice react with the dissolved oxygen and water to form metal hydroxides (in the case of steel, rust is formed) as in Reactions 2.3 and 2.4 ... 

Metals that produce protective oxide layers (such as stainless steels) are especially susceptible to crevice attack. The reduced oxygen concentration in the crevice inhibits repair of the protective oxide film. This is especially true if acidic anions are present, which further retards oxide repair. Stainless steels containing molybdenum are usually less susceptible to attack. 

There is often a period before corrosion starts in a crevice in passivating metals. This so-called incubation period corresponds to the time necessary to establish a crevice environment aggressive enough to dissolve the passive oxide layer. The incubation period is well known in stainless steels exposed to waters containing chloride. After a time period in which crevice corrosion is negligible, attack begins, and the rate of metal loss increases (Fig. 2.8). 

Figure 2.8 Schematic representation of corrosion rate as a function of time in a crevice in stainless steel exposed to chloride-containing water. The time before corrosion initiation is called the incubation period.

The crevice shape markedly affects corrosion. Crevices so tight that water may not enter are entirely immune to attack. In misting environments or alternately wet-diy environments, the crevice holds water and may allow continued attack even when neeu by surfaces eire dry. In sea water, the severity of attack in stainless steel crevices depends on the ratio of the crevice area to the cathodic surface area outside the crevice. If the cathodic area is large relative to crevice eirea, corrosion is promoted. 

Copper alloys often show only weak crevice corrosion. This is especially the case if the copper alloy is coupled to a less noble alloy such as steel. The corrosion of the steel is stimulated by the galvanic effect caused by the coupling of dissimilar metals. Hence, the sacrificial corrosion of the steel protects the copper alloy (Fig. 2.9). See Chap. 16, Galvanic Corrosion. ... 

Figure 2.9 Severely attacked crevice between rolled brass heat exchanger tube and mild steel tube sheet.

Acidic pH helps break down protective oxides on stainless steels. Corrosion usually develops faster and is more severe as pH decreases. At very low pH, however, attack inside crevices may be no more severe than on regions outside the crevice. 

Corrosion products are almost always absent in stainless steel crevices. Areas just outside stainless crevices are stained brown and orange with oxides (Figs. 2.20 and 2.21). Metal ions migrate out of the crevice. Precipitation occurs by reactions similar to Reactions 2.3 and 2.4. Crevice interiors remain relatively free of rust (Figs. 2.16 and 2.17). 

On mild steel and cast irons, rust accumulates at crevice mouths. Darker oxides often are present within crevices (Figs. 2.18 and 2.19). 

Figure 2.23 Shallow pitting in crevice areas on a 304 stainless steel coupon exposed to a misting atmosphere. Note the relatively clean areas where the washer teeth contacted the coupon surface. (Magnification 7.5x.)...

Wastage was caused by crevice corrosion, accelerated by the difference in tube and tube sheet metallurgies. The brass tube, being more noble, was cathodically protected by corrosion of the surrounding mild steel tube sheet. However, the galvanic effect was secondary to the primary cause of failure, namely, crevice corrosion. 

Weld attack. Welds are often more susceptible to corrosion than other areas (see Chap. 15, Welds Defects ). Welds may contain porosity, crevices, high residual stresses, and other imperfections that favor attack. Carbon steel welds are usually ditched by acid attack (Fig. 7.10). 

Figure 15.9 Cross section of stainless steel weld showing crevice corrosion along a site of incomplete fusion. (Magnification 15x.)...

High-alloy steels with >16% Cr" (e.g. 1.4301, AISI 304) Neutral waters and soils (25°C) <0.2 <-0.1 Protection against pitting and crevice corrosion... 

In all cases partial or total hulls of aluminum or stainless steel must be provided with cathodic protection. This also applies to high-alloy steels with over 20% chromium and 3% molybdenum since they are prone to crevice corrosion underneath the coatings. The design of cathodic protection must involve the particular conditions and is not gone into further here. 

Fig. 29. Phosphoric acid etched A606. steel surface showing smut-free, smooth-walled crevice morphology [54].

Residual stresses occur from welding and other fabrication techniques even at very low stress values. Unfortunately, stress relief of equipment is not usually a reliable or practical solution. Careful design of equipment can eliminate crevices or splash zones in which chlorides can concentrate. The use of high-nickel stainless steel alloy 825 (40% nickel, 21% chromium, 3% molybdenum and 2% copper) or the ferritic/austenitic steels would solve this problem. 

Crevice corrosion of copper alloys is similar in principle to that of stainless steels, but a differential metal ion concentration cell (Figure 53.4(b)) is set up in place of the differential oxygen concentration cell. The copper in the crevice is corroded, forming Cu ions. These diffuse out of the crevice, to maintain overall electrical neutrality, and are oxidized to Cu ions. These are strongly oxidizing and constitute the cathodic agent, being reduced to Cu ions at the cathodic site outside the crevice. Acidification of the crevice solution does not occur in this system. 

Copper has excellent resistance to some corrosive environments, including fresh waters and fluoride-containing atmospheres. Alloying is necessary to achieve good strength, but copper limiting with steel for strength is an alternative (BS 5624). Copper and some of its alloys are susceptible to crevice corrosion, but the mechanism is different from that which affects stainless steels. 

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